EP3766084A1 - Compositions for use in impregnation of paper bushings - Google Patents

Compositions for use in impregnation of paper bushings

Info

Publication number
EP3766084A1
EP3766084A1 EP19705973.6A EP19705973A EP3766084A1 EP 3766084 A1 EP3766084 A1 EP 3766084A1 EP 19705973 A EP19705973 A EP 19705973A EP 3766084 A1 EP3766084 A1 EP 3766084A1
Authority
EP
European Patent Office
Prior art keywords
mixture
curable mixture
resin
accelerator
curable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19705973.6A
Other languages
German (de)
French (fr)
Other versions
EP3766084B1 (en
Inventor
Christian Beisele
Hubert WILBERS
Daniel Bär
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huntsman Advanced Materials Licensing Switzerland GmbH
Original Assignee
Huntsman Advanced Materials Licensing Switzerland GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huntsman Advanced Materials Licensing Switzerland GmbH filed Critical Huntsman Advanced Materials Licensing Switzerland GmbH
Priority to PL19705973T priority Critical patent/PL3766084T3/en
Publication of EP3766084A1 publication Critical patent/EP3766084A1/en
Application granted granted Critical
Publication of EP3766084B1 publication Critical patent/EP3766084B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/52—Epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/48—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances fibrous materials
    • H01B3/52—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances fibrous materials wood; paper; press board
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B17/00—Insulators or insulating bodies characterised by their form
    • H01B17/56—Insulating bodies
    • H01B17/58—Tubes, sleeves, beads, or bobbins through which the conductor passes
    • H01B17/583—Grommets; Bushings

Definitions

  • compositions for use in impregnation of paper bushings are provided.
  • the present disclosure relates to compositions for use in impregnation of paper bushings, paper bushings impregnated by such compositions as well as a use of such compositions .
  • Resin impregnated paper (RIP) bushings find use, for example, in high-voltage devices, like high voltage switchgears or transformers.
  • the conductive core of such a bushing is usually wound with paper, with electroplates being inserted between neighboring paper windings.
  • the curable liquid resin/hardener mixture is then introduced into the assembly for impregnation of the paper and cured subsequently.
  • US 3,271,509 A describes electrical insulating material and bushings comprising layers of cellulosic sheet material containing 0.02 - 10 wt . % of a mixture of melamine and dicyandiamide, wherein the ratio of melamine : dicyandiamide is 1 - 5 : 1 - 4, bound together with an infusible mass resulting from the reaction of an epoxy resin with 10 - 60 parts maleic anhydride crosslinking agent per 100 parts epoxy resin, wherein the epoxy resin preferably is 3,4-epoxy-6- methylcyclohexylmethyl-3 , 4-epoxy-methylcyclo-hexane- carboxylate or dicyclopentadiene dioxide.
  • Other crosslinking-agents may, for example, be dodecenylsuccinic, trimellitic or hexahydrophthalic anhydrides. This impregnation system, however, is rather expensive.
  • US 2015/0031789 A1 relates to a composite material for use in high-voltage devices having a high- voltage electrical conductor, at least partially for grading an electrical field of the high-voltage electrical conductor, and comprises a polymeric matrix and fibers embedded therein.
  • Another known system for the production of RIP bushings is based on a BADGE, admixed with a hardener composition containing hexahydrophthalic anhydride (HHPA) and MHHPA.
  • HHPA hexahydrophthalic anhydride
  • MHHPA hexahydrophthalic anhydride
  • the object underlying the present disclosure is to provide an impregnating material for the impregnation of paper bushings, in particular for high-voltage applications, being free of MHHPA and any other materials labeled as toxic substances, however, maintaining the same positive characteristics as known systems, e.g. a Tg of 100 - 130 °C, a similar mechanical strength, a tan delta at 50 Hz of ⁇ 0.3 % at 23 °C, a viscosity of ⁇ 800 mPas at 23 °C and ⁇ 250 mPas at 40 °C and being available at a similar cost level.
  • compositions and/or methods disclosed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of the present disclosure have been described in terms of preferred embodiments, it will be apparent to those having ordinary skill in the art that variations may be applied to the compositions and/or methods and in the steps or sequences of steps of the methods described herein without departing from the concept, spirit, and scope of the present disclosure. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope, and concept of the present disclosure.
  • At least one will be understood to include one as well as any quantity more than one, including but not limited to, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc.
  • the term “at least one” may extend up to 100 or 1000 or more depending on the term to which it refers.
  • the quantities of 100/1000 are not to be considered as limiting since lower or higher limits may also produce satisfactory results.
  • the words “comprising” (and any form of comprising, such as “comprise” and “comprises”) , “having” (and any form of having, such as “have” and “has”) , “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
  • the phrases “or combinations thereof” and “and combinations thereof” as used herein refers to all permutations and combinations of the listed items preceding the term.
  • A, B, C, or combinations thereof is intended to include at least one of: A, B, C, AB, AC, BC, or ABC and, if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB.
  • substantially free shall be used herein to mean present in an amount less than 1 weight percent, or less than 0.1 weight percent, or less than 0.01 weight percent, or alternatively less than 0.001 weight percent, based on the total weight of the referenced composition .
  • ambient temperature refers to the temperature of the surrounding work environment (e.g., the temperature of the area, building or room where the curable composition is used) , exclusive of any temperature changes that occur as a result of the direct application of heat to the curable composition to facilitate curing.
  • the ambient temperature is typically between about 10 °C and about 30 °C, more specifically about 15 °C and about 25 °C.
  • ambient temperature is used interchangeably with “room temperature” herein.
  • a curable mixture comprising a resin mixture of a bisphenol-A-diglycidylether (BADGE) and a bisphenol-F-diglycidylether (BFDGE) , methyltetrahydrophthalic anhydride (MTHPA) as hardener, and an accelerator selected from tertiary alkylamine aminoethylalcohols and/or corresponding ethers thereof.
  • BADGE bisphenol-A-diglycidylether
  • BFDGE bisphenol-F-diglycidylether
  • MTHPA methyltetrahydrophthalic anhydride
  • Non-limiting examples of tertiary alkylamine aminoethylalcohols and/or corresponding ethers thereof include N, N, N' -trimethyl-N -hydroxyethyl- bisaminoethylether, N- ( 3-dimethylaminopropyl ) -N, N- diisopropanolamine, N,N-bis ( 3-dimethylaminopropyl ) -N- isopropanolamine, 2- (2-dimethylaminoethoxy) ethanol, N, N, N'- trimethylaminoethyl-ethanolamine, N, N-dimethylethanolamine, or combinations thereof.
  • the epoxy index according to ISO 3001 of the BADGE is in the range of 3 to 5 eq/kg, preferably in the range of 3.5 to 4.5 eq/kg.
  • the epoxy index according to ISO 3001 of the BFDGE is in the range of 5 to 6.45 eq/kg, preferably in the range of 5.3 and 6.3 eq/kg.
  • the BADGE and the BFDGE are present in the resin mixture at a weight ratio between 1:10 to 10:1.
  • the mixture contains MTHPA in an amount corresponding to 80 wt . % to 120 wt . % of the stoichiometric amount based on the resin mixture, even more preferably, in an amount corresponding to the stoichiometric amount based on the resin mixture.
  • Stoichiometric amount based on the resin mixture means that 1 equivalent of MTHPA is added to 1 equivalent of epoxy resin, i.e., BADGE plus BFDGE.
  • the curable mixture contains the accelerator in an amount of ⁇ 0.2 pbw based on 100 pbw of the resin mixture, more preferably, in an amount of 0.01 to 0.10 pbw based on 100 pbw of the resin mixture.
  • the accelerator is selected from N, N, N' -trimethyl-N ' -hydroxyethyl- bisaminoethylether, N- ( 3-dimethylaminopropyl ) -N, N- diisopropanolamine, N,N-bis ( 3-dimethylaminopropyl ) -N- isopropanolamine, 2- (2-dimethylaminoethoxy) ethanol, N, N, N'- trimethylaminoethyl-ethanolamine, N, N-dimethylethanolamine, or combinations thereof, and preferably is N, N, N'- trimethyl-N -hydroxyethyl-bisaminoethylether .
  • the curable mixture of the present disclosure may contain additional components such as, for example, processing aids, defoamers, rheologic additives, wetting agents, colorants and diluents. It is noteworthy that the compositions disclosed are substantially free of fibers including nano-fibers.
  • the present disclosure also relates to a paper bushing impregnated with the presently disclosed composition .
  • the paper bushing is a bushing for high-voltage application.
  • the present disclosure relates to a use of presently disclosed mixture as an impregnating system for paper bushings, in particular for high-voltage application .
  • the main feature of the present disclosure is the novel use of MTHPA as a main hardener component in compositions for impregnation of paper bushings.
  • the MTHPA used in the presently disclosed curable mixture may be any isomer of MTHPA or mixtures thereof in a purity of >99%.
  • one of the main components of the presently disclosed curable mixture is a resin mixture comprising (i) a BADGE with an epoxy index of 3 to 5 eq/kg and (ii) a BFDGE with an epoxy index of 5 to 6.45 eq/kg as the main resin components.
  • epoxy index refers to the number of moles of epoxy groups per kg of resin.
  • the resins contain at least a portion of longer molecules, i.e. molecules having more than one bisphenol unit. This specific selection results in superior characteristics of the cured products, as can be seen in more detail from the examples .
  • an accelerator that can be used in amounts low enough not to accelerate the curing and release of exotherm too quickly, but, on the other hand, promotes the cure of the resins and the anhydride to achieve a desired high Tg of between about 100 - 130 °C, more particularly 120 to 130 °C.
  • a specifically preferred embodiment comprises the use of N, N, N -trimethyl-N hydroxyethyl-bisaminoethylether or similar amines, such as, for example, N- ( 3-dimethylaminopropyl ) -N, N- diisopropanolamine, N,N-bis (3-dimethylaminopropyl) -N- isopropanolamine, 2- (2-dimethylaminoethoxy) ethanol, N, N, N'- trimethylaminoethyl-ethanolamine, or N, N- dimethylethanolamine, in an amount of ⁇ 0.2 pbw based on 100 pbw of resin.
  • Araldite® MY 740 resin a BADGE with an epoxy index (ISO 3001) of 5.25 to 5.55 eq/kg
  • XB 5860 Resin formulation based on BADGE, containing between 3 - 7 wt . % 4 , 4 ' -Methylene-bis [N, N-bis ( 2 , 3- epoxypropyl) aniline]
  • Aradur® HY 918-1 hardener Mixture of various isomers of MTHPA having a viscosity of 50 - 80 mPas at 25 °C according to ISO 12058
  • Araldite® GY 280 resin a BADGE with an epoxy index (ISO 3001) of 3.57 to 4.45 eq/kg
  • Araldite® GY 281 resin a bisphenol-F-diglycidylether
  • This mixture was then analyzed to determine its viscosity and gel time.
  • a portion of the mixture was then cast into molds (preheated to 80 °C) to prepare test specimens for the mechanical and electrical tests.
  • Tg After cooling to ambient temperature, Tg, mechanical and electrical properties were determined according to the same standard procedures as in Comparative Example 1.
  • Tg After cooling to ambient temperature, Tg, mechanical and electrical properties were determined according to the same standard procedures as in Comparative Example 1.
  • Araldite® GY 281 resin were put in a metal reactor. Then, 180 g of Aradur® HY 918-1 hardener and 0.14 g JEFFCAT® ZF 10 accelerator were added. The components were then mixed with an anchor stirrer at ambient temperature for about 15 min. Finally, the reactor was subjected to a vacuum to remove all or substantially all bubbles.
  • K IC critical stress intensity factor
  • G IC specific break energy
  • Tg was determined according to ISO 6721/94.
  • Tan delta was measured according to IEC 60250.
  • Comparative Example 1 shows the most widely used system in industry: BADGE / MHHPA / BDMA.
  • the main problems of Comparative Example 1 are the REACH issues about MHHPA and the fact that the accelerator BDMA is regarded to be toxic. Further, there is a desire to reduce the tan delta as required by new standards and further reduce the viscosity for more easy impregnation.
  • Comparative Example 2 is a system that avoids the toxicity issues of BDMA, but also contains MHHPA. Therefore, it is no solution to the main issue. Further it has an even higher tan delta compared to Comparative Example 1.
  • the Tg may be increased to the desired level, however, then the reactivity is increased too much and such systems would be by far too reactive to be useful for the targeted applications, such as for example, impregnation systems for resin impregnated paper bushings (the reaction enthalpy would be released too quickly to let it disappear and thus the material temperature would rise too high which leads to overheating and cracks) .
  • Example 1 of the present disclosure shows a way that works in all respects.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Epoxy Resins (AREA)

Abstract

The disclosure relates to a curable mixture for use in impregnation of paper bushings comprising a resin mixture of a bisphenol-A-diglycidylether (BADGE) and a bisphenol-F-diglycidylether (BFDGE), methyltetrahydrophthalic anhydride (MTHPA) as hardener, and an accelerator selected from the group consisting of tertiary alkylamine aminoethylalcohols and corresponding ethers thereof as well as paper bushings impregnated with such mixture and uses of such mixture.

Description

Compositions for use in impregnation of paper bushings
Technical Field
[0001] The present disclosure relates to compositions for use in impregnation of paper bushings, paper bushings impregnated by such compositions as well as a use of such compositions .
Background
[0002] Resin impregnated paper (RIP) bushings find use, for example, in high-voltage devices, like high voltage switchgears or transformers.
[0003] The conductive core of such a bushing is usually wound with paper, with electroplates being inserted between neighboring paper windings. The curable liquid resin/hardener mixture is then introduced into the assembly for impregnation of the paper and cured subsequently.
[0004] There are numerous patents related to such RIP bushings, for example, EP 1 798 740 A1.
[0005] US 3,271,509 A describes electrical insulating material and bushings comprising layers of cellulosic sheet material containing 0.02 - 10 wt . % of a mixture of melamine and dicyandiamide, wherein the ratio of melamine : dicyandiamide is 1 - 5 : 1 - 4, bound together with an infusible mass resulting from the reaction of an epoxy resin with 10 - 60 parts maleic anhydride crosslinking agent per 100 parts epoxy resin, wherein the epoxy resin preferably is 3,4-epoxy-6- methylcyclohexylmethyl-3 , 4-epoxy-methylcyclo-hexane- carboxylate or dicyclopentadiene dioxide. Other crosslinking-agents may, for example, be dodecenylsuccinic, trimellitic or hexahydrophthalic anhydrides. This impregnation system, however, is rather expensive.
[0006] US 2015/0031789 A1 relates to a composite material for use in high-voltage devices having a high- voltage electrical conductor, at least partially for grading an electrical field of the high-voltage electrical conductor, and comprises a polymeric matrix and fibers embedded therein.
[0007] It is also known to use mixtures of a bisphenol- A-diglycidylether (BADGE) , methylhexahydrophthalic anhydride (MHHPA) and benzyldimethylamine (BDMA) for the production of RIP bushings.
[0008] Another known system for the production of RIP bushings is based on a BADGE, admixed with a hardener composition containing hexahydrophthalic anhydride (HHPA) and MHHPA.
[0009] For health and environmental reasons, it is, however, desired to have an impregnating system free of MHHPA, which is classified as SVHC (Substance of Very High Concern) in the REACH Regulations. Object of the Disclosure
[0010] The object underlying the present disclosure is to provide an impregnating material for the impregnation of paper bushings, in particular for high-voltage applications, being free of MHHPA and any other materials labeled as toxic substances, however, maintaining the same positive characteristics as known systems, e.g. a Tg of 100 - 130 °C, a similar mechanical strength, a tan delta at 50 Hz of <0.3 % at 23 °C, a viscosity of <800 mPas at 23 °C and <250 mPas at 40 °C and being available at a similar cost level.
Disclosure
[0011] Unless otherwise defined herein, technical terms used in connection with the present disclosure shall have the meanings that are commonly understood by those having ordinary skill in the art. Further, unless otherwise required by context, singular terms shall include pluralities and plural terms shall include the singular.
[0012] All patents, published patent applications, and non-patent publications mentioned in the specification are indicative of the level of skill of those skilled in the art to which the present disclosure pertains. All patents, published patent applications, and non-patent publications referenced in any portion of this application are herein expressly incorporated by reference in their entirety to the same extent as if each individual patent or publication was specifically and individually indicated to be incorporated by reference to the extent that they do not contradict the instant disclosure.
[0013] All of the compositions and/or methods disclosed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of the present disclosure have been described in terms of preferred embodiments, it will be apparent to those having ordinary skill in the art that variations may be applied to the compositions and/or methods and in the steps or sequences of steps of the methods described herein without departing from the concept, spirit, and scope of the present disclosure. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope, and concept of the present disclosure.
[0014] As utilized in accordance with the present disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings .
[0015] The use of the word "a" or "an", when used in conjunction with the term "comprising", "including", "having", or "containing" (or variations of such terms) may mean "one", but it is also consistent with the meaning of "one or more", "at least one", and "one or more than one".
[0016] The use of the term "or" is used to mean "and/or" unless clearly indicated to refer solely to alternatives and only if the alternatives are mutually exclusive. [0017] Throughout this disclosure, the term "about" is used to indicate that a value includes the inherent variation of error for the quantifying device, mechanism, or method, or the inherent variation that exists among the subject (s) to be measured. For example, but not by way of limitation, when the term "about" is used, the designated value to which it refers may vary by plus or minus ten percent, or nine percent, or eight percent, or seven percent, or six percent, or five percent, or four percent, or three percent, or two percent, or one percent, or one or more fractions therebetween.
[0018] The use of "at least one" will be understood to include one as well as any quantity more than one, including but not limited to, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc. The term "at least one" may extend up to 100 or 1000 or more depending on the term to which it refers. In addition, the quantities of 100/1000 are not to be considered as limiting since lower or higher limits may also produce satisfactory results.
[0019] As used herein, the words "comprising" (and any form of comprising, such as "comprise" and "comprises") , "having" (and any form of having, such as "have" and "has") , "including" (and any form of including, such as "includes" and "include") or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps. [0020] The phrases "or combinations thereof" and "and combinations thereof" as used herein refers to all permutations and combinations of the listed items preceding the term. For example, "A, B, C, or combinations thereof" is intended to include at least one of: A, B, C, AB, AC, BC, or ABC and, if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB.
Continuing with this example, expressly included are combinations that contain repeats of one or more items or terms such as BB, AAA, CC, AABB, AACC, ABCCCC, CBBAAA, CABBB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context. In the same light, the terms "or combinations thereof" and "and combinations thereof" when used with the phrases "selected from" or "selected from the group consisting of" refers to all permutations and combinations of the listed items preceding the phrase.
[0021] The phrases "in one embodiment", "in an embodiment", "according to one embodiment", and the like generally mean the particular feature, structure, or characteristic following the phrase is included in at least one embodiment of the present disclosure, and may be included in more than one embodiment of the present disclosure. Importantly, such phrases are non-limiting and do not necessarily refer to the same embodiment but, of course, can refer to one or more preceding and/or succeeding embodiments. For example, in the appended claims, any of the claimed embodiments can be used in any combination .
[0022] The phrase "substantially free" shall be used herein to mean present in an amount less than 1 weight percent, or less than 0.1 weight percent, or less than 0.01 weight percent, or alternatively less than 0.001 weight percent, based on the total weight of the referenced composition .
[0023] As used herein, the term "ambient temperature" refers to the temperature of the surrounding work environment (e.g., the temperature of the area, building or room where the curable composition is used) , exclusive of any temperature changes that occur as a result of the direct application of heat to the curable composition to facilitate curing. The ambient temperature is typically between about 10 °C and about 30 °C, more specifically about 15 °C and about 25 °C. The term "ambient temperature" is used interchangeably with "room temperature" herein.
[0024] Turning to the present disclosure, the above- noted problem is solved by a curable mixture comprising a resin mixture of a bisphenol-A-diglycidylether (BADGE) and a bisphenol-F-diglycidylether (BFDGE) , methyltetrahydrophthalic anhydride (MTHPA) as hardener, and an accelerator selected from tertiary alkylamine aminoethylalcohols and/or corresponding ethers thereof. [0025] Non-limiting examples of tertiary alkylamine aminoethylalcohols and/or corresponding ethers thereof include N, N, N' -trimethyl-N -hydroxyethyl- bisaminoethylether, N- ( 3-dimethylaminopropyl ) -N, N- diisopropanolamine, N,N-bis ( 3-dimethylaminopropyl ) -N- isopropanolamine, 2- (2-dimethylaminoethoxy) ethanol, N, N, N'- trimethylaminoethyl-ethanolamine, N, N-dimethylethanolamine, or combinations thereof.
[0026] In a preferable embodiment, the epoxy index according to ISO 3001 of the BADGE is in the range of 3 to 5 eq/kg, preferably in the range of 3.5 to 4.5 eq/kg.
[0027] Preferably, the epoxy index according to ISO 3001 of the BFDGE is in the range of 5 to 6.45 eq/kg, preferably in the range of 5.3 and 6.3 eq/kg.
[0028] In one embodiment of the present disclosure, the BADGE and the BFDGE are present in the resin mixture at a weight ratio between 1:10 to 10:1.
[0029] In a preferred embodiment, the mixture contains MTHPA in an amount corresponding to 80 wt . % to 120 wt . % of the stoichiometric amount based on the resin mixture, even more preferably, in an amount corresponding to the stoichiometric amount based on the resin mixture. Stoichiometric amount based on the resin mixture means that 1 equivalent of MTHPA is added to 1 equivalent of epoxy resin, i.e., BADGE plus BFDGE. [0030] Preferably, the curable mixture contains the accelerator in an amount of <0.2 pbw based on 100 pbw of the resin mixture, more preferably, in an amount of 0.01 to 0.10 pbw based on 100 pbw of the resin mixture.
[0031] In one specific embodiment, the accelerator is selected from N, N, N' -trimethyl-N ' -hydroxyethyl- bisaminoethylether, N- ( 3-dimethylaminopropyl ) -N, N- diisopropanolamine, N,N-bis ( 3-dimethylaminopropyl ) -N- isopropanolamine, 2- (2-dimethylaminoethoxy) ethanol, N, N, N'- trimethylaminoethyl-ethanolamine, N, N-dimethylethanolamine, or combinations thereof, and preferably is N, N, N'- trimethyl-N -hydroxyethyl-bisaminoethylether .
[0032] The curable mixture of the present disclosure may contain additional components such as, for example, processing aids, defoamers, rheologic additives, wetting agents, colorants and diluents. It is noteworthy that the compositions disclosed are substantially free of fibers including nano-fibers.
[0033] The present disclosure also relates to a paper bushing impregnated with the presently disclosed composition .
[0034] In one embodiment, the paper bushing is a bushing for high-voltage application.
[0035] Finally, the present disclosure relates to a use of presently disclosed mixture as an impregnating system for paper bushings, in particular for high-voltage application . [0036] The main feature of the present disclosure is the novel use of MTHPA as a main hardener component in compositions for impregnation of paper bushings. The MTHPA used in the presently disclosed curable mixture may be any isomer of MTHPA or mixtures thereof in a purity of >99%.
[0037] Also, one of the main components of the presently disclosed curable mixture is a resin mixture comprising (i) a BADGE with an epoxy index of 3 to 5 eq/kg and (ii) a BFDGE with an epoxy index of 5 to 6.45 eq/kg as the main resin components. As used herein, the term "epoxy index" refers to the number of moles of epoxy groups per kg of resin. In the indicated ranges of epoxy index, the resins contain at least a portion of longer molecules, i.e. molecules having more than one bisphenol unit. This specific selection results in superior characteristics of the cured products, as can be seen in more detail from the examples .
[0038] In the context of such compositions, it is preferred to use an accelerator that can be used in amounts low enough not to accelerate the curing and release of exotherm too quickly, but, on the other hand, promotes the cure of the resins and the anhydride to achieve a desired high Tg of between about 100 - 130 °C, more particularly 120 to 130 °C. Therefore, a specifically preferred embodiment comprises the use of N, N, N -trimethyl-N hydroxyethyl-bisaminoethylether or similar amines, such as, for example, N- ( 3-dimethylaminopropyl ) -N, N- diisopropanolamine, N,N-bis (3-dimethylaminopropyl) -N- isopropanolamine, 2- (2-dimethylaminoethoxy) ethanol, N, N, N'- trimethylaminoethyl-ethanolamine, or N, N- dimethylethanolamine, in an amount of <0.2 pbw based on 100 pbw of resin.
[0039] More details and advantages will become obvious from the following examples. The components, which are all available from Huntsman Corporation or an affiliate thereof (The Woodlands, TX) , used therein are as follows:
Araldite® MY 740 resin: a BADGE with an epoxy index (ISO 3001) of 5.25 to 5.55 eq/kg
Aradur® HY 1102 hardener: MHHPA
Accelerator DY 062 accelerator: BDMA
XB 5860: Resin formulation based on BADGE, containing between 3 - 7 wt . % 4 , 4 ' -Methylene-bis [N, N-bis ( 2 , 3- epoxypropyl) aniline]
Aradur® HY 1235 hardener: Mixture of HHPA and MHHPA
Aradur® HY 918-1 hardener: Mixture of various isomers of MTHPA having a viscosity of 50 - 80 mPas at 25 °C according to ISO 12058
Araldite® GY 280 resin: a BADGE with an epoxy index (ISO 3001) of 3.57 to 4.45 eq/kg
Araldite® GY 281 resin: a bisphenol-F-diglycidylether
(BFDGE ) with an epoxy index (ISO 3001) of 5.80 to 6.30 eq/kg JEFFCAT® ZF 10 accelerator : N, N, N' -trimethyl-N' - hydroxyethyl-bisamino-ethylether
Examples
Comparative Example 1 (BADGE / MHHPA / BDMA)
[0040] 200 g of Araldite® MY 740 resin were put in a metal reactor. Then 180 g of Aradur® HY 1102 hardener and 0.1 g Accelerator DY 062 accelerator were added. The components were then mixed with an anchor stirrer at ambient temperature for about 15 min. Finally, the reactor was subjected to a vacuum to remove all or substantially all bubbles from the mixture.
[0041] This mixture was then analyzed to determine its viscosity and gel time.
[0042] A portion of the mixture was then cast into molds (preheated to 80 °C) to prepare test specimens for the mechanical and electrical tests.
[0043] The molds were treated according to a curing program as indicated in the table below.
[0044] After cooling to ambient temperature, Tg, mechanical and electrical properties were determined according to standard procedures as specified hereunder. Comparative Example 2 (XB 5860 / Aradur® HY 1235 hardener)
[0045] 200 g of XB 5860 were put in a metal reactor. Then 170 g of Aradur® HY 1235 hardener were added. The components were then mixed with an anchor stirrer at ambient temperature for about 15 min. Finally, the reactor was subjected to a vacuum to remove all or substantially all bubbles from the mixture.
[0046] This mixture was then analyzed to determine viscosity and gel time.
[0047] A portion of the mixture was then cast into molds (preheated to 80 °C) to prepare test specimens for the mechanical and electrical tests.
[0048] The molds were treated according to a curing program as indicated in the table below.
[0049] After cooling to ambient temperature, Tg, mechanical and electrical properties were determined according to the same standard procedures as in Comparative Example 1.
Comparative Example 3 (Araldite® MY 740 resin / Aradur® HY 918-1 hardener / 0.05 pbw BDMA)
[0050] 200 g of Araldite® MY 740 resin were put in a metal reactor. Then 170 g of Aradur® HY 918-1 hardener and 0.1 g Accelerator DY 062 accelerator were added. The components were then mixed with an anchor stirrer at ambient temperature for about 15 min. Finally, the reactor was subjected to a vacuum to remove all or substantially all bubbles from the mixture.
[0051] This mixture was then used to determine viscosity and gel time.
[0052] A portion of the mixture was then cast into molds (preheated to 80 °C) to prepare test specimens for the mechanical and electrical tests.
[0053] The molds were treated according to a curing program as indicated in the table below.
[0054] After cooling to ambient temperature, Tg, mechanical and electrical properties were determined according to the same standard procedures as in Comparative Example 1.
Comparative Example 4 (Araldite® MY 740 resin / Aradur® HY 918-1 hardener / 0.2 pbw BDMA)
[0055] 200 g of Araldite® MY 740 resin were put in a metal reactor. Then 170 g of Aradur® HY 918-1 hardener and 0.4 g Accelerator DY 062 accelerator were added. The components were then mixed with an anchor stirrer at ambient temperature for about 15 min. Finally, the reactor was subjected to a vacuum to remove all or substantially all bubbles from the mixture.
[0056] This mixture was then used to determine viscosity and gel time. [0057] A portion of the mixture was then cast into molds (preheated to 80 °C) to prepare test specimens for the mechanical and electrical tests.
[0058] The molds were treated according to a curing program as indicated in the table below.
[0059] After cooling to ambient temperature, Tg, mechanical and electrical properties were determined according to the same standard procedures as in Comparative Example 1.
Example 1
[0060] 160 g of Araldite® GY 280 resin and 40 g of
Araldite® GY 281 resin were put in a metal reactor. Then, 180 g of Aradur® HY 918-1 hardener and 0.14 g JEFFCAT® ZF 10 accelerator were added. The components were then mixed with an anchor stirrer at ambient temperature for about 15 min. Finally, the reactor was subjected to a vacuum to remove all or substantially all bubbles.
[0061] This mixture was then used to determine viscosity and gel time.
[0062] A portion of the mixture was then cast into molds (preheated to 80 °C) to prepare test specimens for the mechanical and electrical tests.
[0063] The molds were treated according to a curing program as indicated in the table below. [0064] After cooling to ambient temperature, Tg, mechanical and electrical properties were determined according to the same standard procedures as in Comparative Example 1. [0065] The formulations as well as the results of the various measurements are shown in the table below.
[0066] Tensile strength and elongation at break were determined at 23 °C according to ISO R527.
[0067] Flexural strength were determined at 23 °C according to ISO 178.
[0068] KIC (critical stress intensity factor) in and GIC (specific break energy) in J/m2 were determined at 23 °C by bend notch experiment.
[0069] Tg was determined according to ISO 6721/94.
[0070] Tan delta was measured according to IEC 60250.
[0071] Comparative Example 1 shows the most widely used system in industry: BADGE / MHHPA / BDMA. The main problems of Comparative Example 1 are the REACH issues about MHHPA and the fact that the accelerator BDMA is regarded to be toxic. Further, there is a desire to reduce the tan delta as required by new standards and further reduce the viscosity for more easy impregnation.
[0072] Comparative Example 2 is a system that avoids the toxicity issues of BDMA, but also contains MHHPA. Therefore, it is no solution to the main issue. Further it has an even higher tan delta compared to Comparative Example 1.
[0073] The most simple idea to the person skilled in the art of formulation RIP systems might be just to exchange BADGE/ MHHPA/ BDMA with MTHPA instead of MHHPA. Comparative Example 3, however, shows that this would not work because the Tg would be by far too low.
[0074] By increasing the amount of BDMA, the Tg may be increased to the desired level, however, then the reactivity is increased too much and such systems would be by far too reactive to be useful for the targeted applications, such as for example, impregnation systems for resin impregnated paper bushings (the reaction enthalpy would be released too quickly to let it disappear and thus the material temperature would rise too high which leads to overheating and cracks) .
[0075] Example 1 of the present disclosure shows a way that works in all respects. Combining selected types of BADGE and BFDGE to form a resin mixture and curing the resin mixture with MTHPA, accelerated by a small amounts (< 0.2 %) of tertiary alkylamine aminoethylalcohols or ethers thereof, such as the preferred catalyst JEFFCAT® ZF 10 accelerator, instead of BDMA, results in a cost efficient system that is low viscous, sufficiently low reactive (to prevent overheating in the final application) , resulting in a Tg >120 °C, providing the desired low tan delta of <0.3 %, and free of materials currently labeled as toxic substances by , such as MHHPA and free bisphenol A. Being free of such toxic materials should render the presently disclosed composition as REACH compliant. Additional, the presently disclosed composition delivers a better mechanical profile than the presently most widely used system of Comparative Example 1. [0076] The above-disclosed subject matter is to be considered illustrative, and not restrictive, and the appended claims are intended to cover all such modifications, enhancements, and other embodiments, which fall within the true scope of the present disclosure. Thus, to the maximum extent allowed by law, the scope of the present disclosure is to be determined by the broadest permissible interpretation of the following claims and their equivalents, and shall not be restricted or limited by the foregoing detailed description.

Claims

Claims
1. A curable mixture for use in impregnation of paper bushings comprising (i) a resin mixture comprising a bisphenol-A-diglycidylether (BADGE) and a bisphenol-F- diglycidylether (BFDGE), (ii) methyltetrahydrophthalic anhydride (MTHPA) as hardener, and (iii) an accelerator selected from tertiary alkylamine aminoethylalcohols and/or corresponding ethers thereof.
2. The curable mixture according to claim 1, wherein the epoxy index according to ISO 3001 of the BADGE is in the range between 3 and 5 eq/kg.
3. The curable mixture according to claim 2, wherein the epoxy index according to ISO 3001 of the BADGE is in the range between 3.5 and 4.5 eq/kg.
4. The curable mixture according to any of the preceding claims, wherein the epoxy index according to ISO 3001 of the BFDGE is in the range between 5 and 6.45 eq/kg.
5. The curable mixture according to claim 4, wherein the epoxy index according to ISO 3001 of the BFDGE is in the range between 5.3 and 6.3 eq/kg.
6. The curable mixture according to any of the preceding claims, wherein the BADGE and the BFDGE are present in the resin mixture at a weight ratio between 1:10 to 10:1.
7. The curable mixture according to any of the preceding claims, wherein the curable mixture contains MTHPA in an amount corresponding to 80 wt . % to 120 wt . % of the stoichiometric amount based on the resin mixture.
8. The curable mixture according to claim 7, wherein the curable mixture contains MTHPA in amount corresponding to the stoichiometric amount based on the resin mixture.
9. The curable mixture according to any of the preceding claims, wherein the curable mixture contains the accelerator in an amount of <0.2 pbw based on 100 pbw of the resin mixture.
10. The curable mixture according to claim 9, wherein the curable mixture contains the accelerator in an amount of 0.01 to 0.10 pbw based on 100 pbw of the resin mixture.
11. The curable mixture of any of the preceding claims, wherein the accelerator is selected from N, N, N'- trimethyl-N -hydroxyethyl-bisaminoethylether, N- (3- dimethylaminopropyl ) -N, N-diisopropanolamine, N,N-bis (3- dimethylaminopropyl ) -N-isopropanolamine, 2- (2- dimethylaminoethoxy) ethanol, N, N, N' -trimethylaminoethyl- ethanolamine, N, N-dimethylethanolamine, or combinations thereof .
12. The curable mixture of claim 11, wherein the accelerator is N, N, N' -trimethyl-N -hydroxyethyl-bisaminoethylether .
13. A paper bushing impregnated with a composition according to any of the preceding claims.
14. The paper bushing according to claim 13, wherein the paper bushing is a bushing for high-voltage application.
15. Use of a mixture according to any of claims 1 to 10 as an impregnating system for paper bushings, in particular for high-voltage application.
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Publication number Priority date Publication date Assignee Title
US3271509A (en) 1963-04-12 1966-09-06 Westinghouse Electric Corp Electrical insulation for condenser bushings and the like
EP0523001A1 (en) 1991-06-20 1993-01-13 Ciba-Geigy Ag Curable epoxy resin composition containing a blocked accelerator
JPH1160696A (en) * 1997-08-14 1999-03-02 Tosoh Corp Epoxy resin composition
EP1754733A1 (en) * 2005-07-26 2007-02-21 Huntsman Advanced Materials (Switzerland) GmbH Composition
ATE522912T1 (en) 2005-12-14 2011-09-15 Abb Research Ltd HIGH VOLTAGE FEEDBACK
EP1978049B1 (en) * 2007-04-03 2010-02-24 ABB Research Ltd Curable Epoxy Resin Composition
CA2835658C (en) 2011-05-13 2020-01-28 Dow Global Technologies Llc Insulation formulations
WO2013017149A1 (en) * 2011-07-29 2013-02-07 Abb Research Ltd Curable epoxy resin composition
ITTO20111208A1 (en) 2011-12-23 2013-06-24 Bridgestone Corp RUBBER COMPOUND FOR TIRES
KR102172296B1 (en) * 2014-04-30 2020-10-30 엘지이노텍 주식회사 Epoxy resin composite and printed curcuit board comprising insulating layer using the same
WO2017157591A1 (en) 2016-03-15 2017-09-21 Huntsman Advanced Materials Licensing (Switzerland) Gmbh A process for the preparation of insulation systems for electrical engineering, the articles obtained therefrom and the use thereof
DE102016006910A1 (en) * 2016-06-08 2017-12-14 Hexion GmbH Composition containing a polymer based on epoxy compounds
JP2018012745A (en) * 2016-07-19 2018-01-25 住友ベークライト株式会社 Epoxy resin composition for casting and electric/electronic component

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US20210024684A1 (en) 2021-01-28

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